The present invention concerns a high temperature process for preparing alkyUithium compounds containing 2 to 16 carbon atoms by reacting lithium metal with alkyl halides at temperatures of 35 to 120°C.

Methods of preparation of alkyllithiums have been published by various workers in the field, such as, for example, C.W. Kamienski et al. U.S. Patent 3,452,112. A process for producing alkyUithium containing six or more carbon atoms, such as octyllithium is disclosed by C. Guo and coworkers, J. Am. Che . Soc, 1985, 107, 6030 who employed a refluxing hexane medium and a four hour post addition reflux to obtain a yield of about 70%. High purity concentrated alkyllithiums are highly desired as it is important that the alkyUithium product be free from or at least low in olefin content as olefins lead to the development of deep yellow colored alkyUithium products. The level of chloride ion impurities is important as high chloride values of 300 ppm and above generally occur in hazy alkyUithium products. While concentrated, clear solutions of alkyllithiums in hydrocarbon solvents are clearly desirable, they are difficult to obtain. One reason for this is that concentrated solutions of alkyUithium compounds are highly viscous so that unreacted excess lithium generally employed in the reaction is very difficult to remove by filtration or other conventional particle separation means. The prior art processes produce alkyUithium compounds containing over 300 parts per million of dissolved inorganic halides, generally lithium chloride, which is not removed by filtration. When these dilute solutions are concentrated by distillation or other solvent solvent removal means, the lithium halide forms fine crystals in the product solution which gives the product a hazy rather than

clear appearance and in some instances, the halide precipitates. High yields of alkyUithium, 90% or greater, is highly desirable economically.

The present invention provides an improved process for producing alkyUithium in high yields and high purity by reacting a primary alkyl halide with lithium metal in a liquid hydrocarbon solvent in an inert atmosphere to obtain yields of alkyllithiums of at least 90% by reacting an alkyl halide containing 2 to 16 carbon atoms and mixtures thereof with finely divided lithium metal in a hydrocarbon solvent at a temperature between 35 and 125 degrees centigrade.

The preferred reaction temperatures vary from com¬ pound to compound, with each compound having its own preferred conditions. Surprisingly, within a preferred temperature range for an alkyl halide/lithium metal reaction, the most preferred reaction condition occurs at reflux conditions. For example, the reaction that produces butyllithium conducted at 35°C and 50°C under reflux conditions results in higher yields and higher purity than are achieved when conducting the same reaction at 35°C or 50°C under non-reflux conditions. This can be seen in the Table by comparing Run 7742 with Run 7743 and Run 7746 with Run 7747. Comparison of Run 7742 with 7743 illustrates that in the lower temperature range, reacting at reflux (35°C) , improves the yield and slightly decreases the soluble chloride level. Comparison of Runs 7746 and 7747 illustrate that near the middle of the temperature range, 50°C, reacting at reflux increases the yield and significantly decreases the soluble chloride level. The increase in yield of butyllithium with increasing temperature can also be seen in Figure 1, a plot of yield versus temperature for the lithium metal butylchloride reaction to produce butyllithium, showing a.preferred range of 35° to 60°C

and most preferably at 50°C.

The use of high reaction temperatures in alkylchloride/lithium reactions not only improves yields of the alkyUithium but also improves reaction initiation and promotes completion of the respective alkyl chloride reactions, thus decreasing the the by¬ product coupling and disproportionation reactions. These phenomena are evident, not only by the increased yields obtained, but also by the lower amounts of dissolved inorganic chloride and olefins present in the product solutions. The Table 1 data generally support the conclusion that for a selected alkyl chloride the yield improves as the reaction temperature is increased. However, there is for each alkyl chloride an optimum temperature which, if exceeded, causes the yield to decrease. n-Butyl chloride reacted with lithium in refluxing solvents is shown in Figure 3 to increase to a high yield of 98.5% at about 50°C and to decrease slightly at 70°C to 95.3%. When this butylchloride- lithium metal reaction is done in toluene at 80°C the yield drops to 86.6 (Run 7824).

The lithium metal used in this process can be any clean lithium metal and preferably containing 0.4 to 0.76% sodium. Excess lithium metal in amounts of up to 10% by weight above stoichiometric amounts are used to insure reaction of all the alkyl chloride used in a reaction. To best achieve the benefits of this process the lithium metal is used in particulate form, preferably less than 300 microns in size, most preferably 10 to 300 microns in size. Typically commercially available lithium dispersions containing 0.5 to 0.76% sodium are used but pure lithium metal dispersions can also be successfully employed.

The alkyl halides used in this process are typically made from alcohols so the alkyl halides may contain some

residual alcohol which may be catalytic. All examples in this application were conducted with commercially available alkyl halides. The useful alkyl halides contain 2 to 16 carbon atoms and the halide ion may be bromo, chloro or iodo with chloro being preferred as being less expensive and more generally available.

Solvents suitable for use in the process of this invention include liquid saturated aliphatic and cyclo- aliphatic hydrocarbons containing 5 to 12 carbon atoms such as isopentane, n-pentane, n-hexane, n-heptane, 2- ethylhexane, iso-octane, n-octane, decane, dodecane and the like or saturated cyclic hydrocarbons containing 5 to 12 carbon atoms such as cyclopentane or methylcyclo- hexane and the like and mixtures thereof. Aromatic hydrocarbons containing 6 to 12 carbon atoms such as benzene, toluene, n-propyl benzene, isopropylbenzene, xylenes 1,2,3 ,4,tetrahydro naphthalene and the like may also be used. Since reflux conditions and optimum reaction temperatures are related hydrocarbon mixtures are quite useful. Nevertheless, a single liquid hydrocarbon may be more desirable than mixed hydrocarbons.

As noted above reaction temperatures of 35 to 125°C can be employed and while each alkyl halide has its own preferred reaction temperature curve and specific best reaction temperature the best results are obtained under reflux conditions. Long reaction times can be used at lower temperatures but give poor results than are achieved under reflux conditions. The alkyl halide feed rate can be varied. Slow alkyl halide feed rates with external heat may be used; heat may be applied to help initiate the reaction and the feed rate adjusted to control the exothermic reaction. Reaction initiation is faster if the lithium metal/hydrocarbon mixture is at the reflux temperature of the solvent when the alkyl

halide feed is started but no major increases in yields occur from this procedure. The reaction media should be cooled or allowed to cool to ambient conditions once the reaction is completed. The post reaction heating taught by Meals, J. Org. Chem. , 9_, pp 211-218 (1944) should be avoided.

Numerous experiments were conducted under inert conditions employing various commercially available alkyl chlorides and commercially available lithium metal dispersions having particles sizes of less than 300 microns. The lithium dispersion was washed in solvent to remove the dispersing oil and rinsed until the metal was clean, free of oil. The clean metal was added to the selected solvent in a reactor equipped with a reflux condenser, a stirrer, a feed device for adding the alkyl chloride and means for heating the reactor and reaction mass. Surprisingly, the metal conditioner taught by Kamienski et al. in U.S. Patent 3,452,112 is not needed in the present process. The lithium-solvent mixture was stirred and heated to the selected reaction temperature, often the reflux temperature of the solvent, and the alkyl chloride feed was started. Thereafter, the temperature was controlled by the rate of alkyl chloride addition. Process variables such as reaction temperatures, halide feed rate, excess lithium, percent sodium in the lithium, washing the lithium and the effect these variables have on yield and purity were extensively studied. The reactions are conducted in an inert atmosphere. The results are contained in the various figures and the Table which summarizes a wide variety of compounds and conditions. In general the table shows yields and optimal temperature for each alkyl halide. Optimal temperatures for each alkyl chloride produces minimal soluble chloride levels. The chloride analytical technique used had a lower detection

limit of <13 ppm.

Figure 1 - This plot shows the % yield of n-butyl lithium ( ) prepared in hexane using 10% excess lithium containing 0.48% sodium at several temperatures increases in yield with increasing temperature. Figure 2 - This plot shows the results of a comparable series of experiments in which the solvent used was toluene. Again, increasing temperature definitely increased yield. The lithium contained 0.76% sodium. "Dry" toluene, 30 ppm H2O (0) and "wet" toluene, 226 ppm H2O (+) .

Figure 3 shows a series of n-butyl lithium experi¬ ments using 10% excess lithium (0.48% Na) in refluxing solvents: pentane boiling point (BP) 36.1°C (0), cyclopentane BP 49.3°C (+) and hexane BP 68.7°C (*) . Figure 3 clearly shows the yield increasing with temperature but then starting to decrease with further increasing temperature.

Figure 4 shows the results of varying the feed rate of n-butyl chloride dispersion in hexane. At 35°C (*) the yield gradually increased although very slightly. At reflux (0) there is no change in yield at short feed times, 0.5 to 1.5 hours, but the yield drops at longer feed times. Figure 5 - This plot shows results of varying the amount of lithium metal in producing n-butyllithium. Yield drop off is only slightly less sensitive to reaction temperature at reflux (0) compared to reaction at 35°C (*) , about a 1% decrease at reflux versus a 2% drop off at 35°C. Greater than 10 mole % excess lithium results in same yield improvement.

Figure 6 - This plot shows that n-butyllithium yields decrease significantly at alloyed levels of sodium in the lithium metals below 0.3 to 0.4% when the butyl chloride/lithium reaction is conducted at 35°C (*)

but there is no decrease at reflux ( ) .

Figure 7 - This plot shows that, as the reaction temperatures are increased in hexane, soluble inorganic chloride levels in the n-butyllithium product decrease significantly (*) .

Figure 8 - This plot shows that, as the reaction temperatures (*) are increased in toluene, soluble inorganic chloride levels in the n-butyllithium product decrease significantly. Figure 9 - This plot shows an optimum hexyllithium yield in refluxing solvents at about 70°C. Cyclopentane (+) , hexane (o) , cyclohexane (D) and heptane (x) .

Figure 10 - This plot shows octyllithium yields in refluxing solvents are highest between 70 and 80°C. Solvents employed: cyclopentane (o) , hexane (+) , cyclohexane (*) and heptane (D) .

Figure 11 - This plot shows the yields of 2- ethylhexyllithiu in various refluxing solvents. Solvents employed were cyclohexane (o) , heptane (+) , cyclopentane (*) and octane (o) .

Figure 12 - This plot further emphasizes the excellent yields of various alkyllithiums obtained in refluxing hexane. The alkyllithiums tested were butyl, hexyl, octyl, decyl and dodecyllithium. Figure 13 shows that n-hexyllithium chloride values are lower when the reaction is done at a higher temperature.

The following examples further illustrate the invention. Unless noted otherwise all examples were conducted in an inert argon atmosphere.

EXAMPLE 1 PREPARATION OF n-BUTYLLITHIUM AT ELEVATED TEMPERATURE Run 7739

The reactor and apparatus consisted of a 500 ml Morton Cleaved 3 necked flask equipped with a reflux condensor, y tube for additions, 125 ml pressure- equalizing addition (dropping) funnel, stirring shaft with teflon blade, stirring motor, a thermometer probe with an electronic read out and means for maintaining an inert atmosphere in the reactor.

A commercially available lithium metal dispersion having a particle size of less than 300 microns was hexane washed twice and pentane washed once and dried with Argon. The metal was then weighed, 12.10g (1.743 moles) .

Hexane, 310 illiliters, was used to transfer the lithium through a transfer tube to the reactor. The hexane-lithiu mixture was heated to reflux (Dry

Ice/hexane in condensor) and dropwise feed of n-butyl chloride begun. The reaction proceeded instantaneously (heavy refluxing) and the source of heat was removed. The 73.4g of n-butylchloride (0.7924 moles) was fed in over a 40 minute period, the reaction heat controlled strictly by the rate of reflux. The reaction mixture was allowed to cool to ambient, with stirring, over a 2.5 hour period. The mixture was filtered and the lithium chloride residue washed three times with hexane (50 ml each) over a 25-30 minute period. The combined filtrate and washings were weighed. A sample of the product solution was assayed for total contained alkalinity and color index was determined and the yield of n-butyllithium was calculated.

EXAMPLE 2

ELEVATED TEMPERATURE, REFLUX EXAMPLE

Run 7622, 414-43

1-HEXYLLITHIUM HEXANE

A 500 ml, three-necked Morton flask was fitted with a mechanical stirrer, a 250 ml, pressure-equalizing addition funnel, and a Claisen adapter equipped with a reflux condenser, a thermocouple, and an argon inlet. This apparatus was dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium dispersion, 22.00 g (3.17 mole, 20 % excess Li, 2.40 equivalents) was washed free of mineral oil with hexane (2 x 100 ml) , pentane (1 x 100 ml) , dried in a stream of argon, then transferred to the flask with 210 ml of hexane. The resultant slurry was stirred at 470 RPMs and heated to 66°C. After reflux was established, the heat source was removed. 1- Hexyl chloride, 159.32 g (1.32 mole, 1.00 equivalent), was added dropwise through the addition funnel. The reaction temperature rose rapidly to reflux. The reaction mixture was maintained at reflux by adjustment of the halide feed rate. The total halide feed time was 3.25 hours. At the end of the feed, the reaction temperature rapidly declined. The reaction mixture was stirred for one hour at 470 RPMs, two hours at 300 RPMs, then transferred to a scintered glass filter. The solution filtered very rapidly, 300 ml of filtrate was collected in 1.5 minutes at 2 psi argon. The solids were reslurried with fresh hexane (2 x 50 ml) , and these washes were combined with the main filtrate. This afforded a clear, dark yellow solution, yield = 450 ml, 329.5 g. Total base = 34.9% Active C-Li = 34.7%

The yield based on the active C-Li (carbon-lithium) analysis was 94.1%

Soluble Cl (chloride) <26 ppm

EXAMPLE 3

ELEVATED TEMPERATURE, NON-REFLUX EXAMPLE

Run 7853, 442-3

2-ETHYLHEXYLLITHIUM IN HEPTANE

A one liter, three-necked Morton flask was fitted with a mechanical stirrer, a 250 ml, pressure-equalizing addition funnel, and a Claisen adapter equipped with a reflux condenser, a thermocouple, and an argon inlet. This apparatus was dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium dispersion, 18.50 g (2.67 mole, 20% excess Li, 2.40 equivalents) was washed free of mineral oil with pentane three times (3 x 100 ml) , dried in a stream of argon, then transferred to the flask with 400 ml of heptane. The resultant slurry was stirred at 470 RPMs, then heated to 70°C with a heating mantle. The mantle was then removed, and 2-ethylhexyl chloride, 165.03 g (1.11 mole, 1.00 equivalent), was added dropwise through the addition funnel. The reaction temperature slowly rose, after approximately 3% of the feed had been added. The temperature was maintained between 70°C and 75°C with intermittent cooling from an hexane / dry ice cooling bath. The total halide feed time was 2.25 hours. At the end of the feed, the reaction temperature rapidly declined. The reaction mixture was stirred for one hour at 470 RPMs, one hour at 300 RPMs, then transferred to a scintered glass filter. The solution filtered very rapidly, 600 ml of filtrate was collected in one minute at 2 psi argon. The solids were reslurried with fresh heptane (65 ml, 60 ml) , and these washes were combined with the main filtrate. This afforded a clear, colorless solution, yield = 700 ml, 480.4 g.

Total base = 27.3% Active C-Li = 27.3%

The yield based on the active C-Li analysis was 98.4% Soluble Cl <13 ppm.

EXAMPLE 4

ELEVATED TEMPERATURE, REFLUX EXAMPLE

Run 8507, 442-60

1-OCTYLLITHIUM IN HEXANE

A one liter, three-necked Morton flask was fitted with a mechanical stirrer, a 250 ml pressure-equalizing addition funnel, and a Claisen adapter equipped with a thermocouple, a reflux condenser, and an argon inlet.

This apparatus was dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium dispersion, 20.50 g (2.953 mole, 20% excess Li, 2.40 equivalents) was washed free of mineral oil with hexane 2 x 100 ml) pentane (1 x 100 ml) , dried in a stream of argon, then transferred to the reaction flask with 450 ml of hexane. The resultant slurry was stirred at 450 RPMs, and heated to 67°C with a heating mantle controlled with a variac. After reflux was established, the heat source was removed. 1-

Chlorooctane, 182.97 g (1.231 mole, 1.00 equivalent) was added dropwise through the addition funnel. An immediate exotherm was observed. The reaction temperature rose rapidly to reflux. The reaction mixture was maintained at reflux by adjustment of the halide feed rate. The total halide feed time was 100 minutes. The reaction temperature declined rapidly at the end of the halide feed. The reaction mixture was stirred for one hour at 450 RPMs, 1.25 hours at 300 RPMs, then transferred to a dry, scintered glass filter

with argon pressure. The solution filtered very rapidly, as 550 ml of filtrate was collected in 2.167 minutes at 3 psi argon. The solids were reslurried with fresh hexane (2 x 75 ml) , and these washes were combined with the main filtrate.

This afforded a clear, pale yellow solution, yield = 790 ml, 548.7 g.

Total base = 25.6%.

Active C-Li = 24.6% The yield based on the active C-Li (carbon-lithium) analysis was 91.4%. Soluble Cl (chloride) = 31 ppm.

A one ml aliquot of this solution was hydrolyzed with water at low temperature. The organic layer was analyzed by Gas Chromatography. The components were identified by co-elution with authentic standards. The composition of the hydrolyzed sample was analyzed as: n=octane (93.84%), 1-chlorooctane (1.77%), and side reaction products (coupling, disproportionation) (4.38%).

COMPARISON EXAMPLE A Run 7605 414-32 1-HEXYLLITHIUM IN HEXANE

A 500 ml, three-necked Morton flask was fitted with a mechanical stirrer, a 250 ml, pressure-equalizing addition funnel, and a Claisen adapter equipped with a reflux condenser, a thermocouple, and an argon inlet. This apparatus was dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium dispersion, 9.00 g (1.30 mole, 20% excess, 2.40 equivalents), pentane (1 x 100 ml) , dried in a stream of argon, then transferred to the flask with 170 ml of hexane. The resultant slurry was

stirred at 470 RPMs. 1-Hexyl chloride, 65.13 g (0.54 mole, 1.00 equivalent), was added dropwise through the addition funnel. The reaction temperature slowly rose, after approximately 3% of the feed had been added. The temperature was maintained between 30°C and 35°C with intermittent cooling from an hexane / dry ice cooling bath. The total halide feed time was 2 hours. At the end of the feed, the reaction temperature rapidly declined. The reaction mixture was stirred for thirty minutes at 470 RPMs, 1.5 hours at 300 RPMs, then transferred to a scintered glass filter. The solids were reslurried with fresh hexane (2 x 35 ml) , and these washes were combined with the main filtrate. This afforded a clear, pale yellow solution, yield = 240 ml, 168.4 g.

Total base = 24.6%

Active C-Li = 24.6%

The yield based on the active C-Li analysis was 81.7%.

Soluble Cl 302 ppm.

COMPARISON EXAMPLE B Run 8518, 442-63 1-OCTYLLITHIUM IN HEXANE

A one liter, three-necked Morton flask was fitted with a mechanical stirrer, a 250 ml pressure-equalizing addition funnel, and a Claisen adapter equipped with a thermocouple, a reflux condenser, and an argon inlet. This apparatus was dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium dispersion, 21.50 g (3.098 mole, 20% excess Li, 2.40 equivalents) was washed free of mineral oil with hexane (3 x 100 ml) , pentane (1 x 100 ml) , dried in a stream of argon, then transferred

to the reaction flask with 480 ml of hexane. The resultant slurry was stirred at 450 RPMs, and heated to 35°C with a heat gun. The heat source was removed. 1- Chlorooctane, 191.95 g (1.291 mole, 1.00 equivalent) was added dropwise through the addition funnel. An exotherm was noted after 2% of the feed had been added. The reaction mixture was maintained at 30-35°C by a dry ice/hexane cooling bath. The total halide feed time was 108 minutes. The reaction temperature declined rapidly at the end of the halide feed. The reaction mixture was stirred for one hour at 450 RPMs, 1.25 hours at 300 RPMs, then transferred to a dry, scintered glass filter with argon pressure. The solution filtered very slowly, as 550 ml of filtrate was collected in 15 minutes at 3 psi argon. The solids were reslurried with fresh hexane (2 x 75 ml) , and these washes were combined with the main filtrate.

This afforded a clear, pale yellow solution, yield = 800 ml, 563.8 g. Total base = 23.9%. Active C-Li = 23.3%

The yield based on the active C-Li (carbon-lithium) analysis was 84.8%. Soluble Cl (chloride) = 208 ppm. A one ml aliquot of this solution was hydrolyzed with water at low temperature. The organic layer was analyzed by Gas Chromatography. The components were identified by co-elution with authentic standards. The composition of the hydrolyzed sample was n-octane (81.14%), 1-chlorooctane (4.31%), and side reaction products (coupling disproportionation) (11.55%) .

TABLE

\ RXN TEMP SOL, CL

RXN HALIDE SOLVENT ,O C, YIELD (ppm) COMMENTS

7728 n-Butylchloride Hexane 35 91.9 240

7730 n-Butylchloride Hexane 35 91.6 289

7743 n-Butylchloride Hexane 35 90.1 398

7746 n-Butylchloride Hexane 50 93.7 299

7752 n-Butylchloride Hexane 50 93.7 124

7755 n-Butylchloride Hexane 50 94.8

7812 n-Butylchloride Hexane 70 95.2 30 Reflux

7813 n-Butylchloride Hexane 70 94.7 30 Reflux

7840 n-Butylchloride Hexane 70 95.5 <13 Reflux

7843 n-Butylchloride Hexane 70 95.9 <13 Reflux

7945 n-Butylchloride Hexane 70 96.1 <13 Reflux

7849 n-Butylchloride Hexane 70 95.5 13 Reflux

7742 n-Butylchloride Pentane 35 95.9 378 Reflux

7747 n-Butylchloride Cyclopentane 50 98.5 135 Reflux

7756 n-Butylchloride Toluene 20 90.5 304

7712 n-Butylchlor ide Toluene 35 95.2 252

7733 n-Butylchloride Toluene 35 94.6

7753 n-Butylchloride Toluene 50 97.4 64

7788 n-Butylchloride Toluene 50 97.9 86

7748 n-Butylchloride Toluene 60 99.2 16

7749 n-Butylchloride Toluene 60 95.9 94

7824 n-Butylchloride Toluene 80 86.6 20

7864 1 -Chloro-2-methylbutane Hexane 70 98.4 <13 Reflux

7605 1 -Chlorohexane Hexane 35 81.7 302

7622 1 -Chlorohexane Hexane 70 94.1 <26 Reflux

7650 1 -Chlorohexane Hexane 70 94.0 27 Reflux

7905 1 -Chlorohexane Hexane 70 93.7 62 Reflux

7713 1 -Chlorohexane Cyclopentane 50 85.4 205 Reflux

7696 1 -Chlorohexane Cyclohexane 80 80.2 .-26 Reflux

7691 1 -Chlorohexane Heptane 100 46.1 15210 Reflux

7701 1 -Chlorohexane Heptane 70 93.9 48

7871 1 -Chlorohexane Toluene 60 98.1 15

7863 1-Chloroheptane Hexane 70 95.0 <13 Reflux

RX TEMP SOL. CL

RXN HALIDE SOLVENT tO C) YIELD (ppm) COMMENTS

7734 1 -Chlorooctane Cyclopentane 50 87.6 250 Reflux

8516 1 -Chlorooctane Hexane 35 83.0 158

8518 1 -Chlorooctane Hexane 35 84.8 208

7629 1 -Chlorooctane Hexane 70 95.4 90 Reflux

8507 1 -Chlorooctane Hexane 70 91.4 31 Reflux

8512 1 -Chlorooctane Hexane 70 91.8 38 Reflux

7685 1 -Chlorooctane Cyclohexane 80 95.3 <21 Reflux

7681 1 -Chlorooctane Heptane 100 75.8 379 Reflux

7714 1 -Chloro-2-ethylhexane Cyclopentane 50 93.3 25 Reflux

7853 1 -Chloro-2-ethylhexane Heptane 70 98.4 <13

7678 1 -Chloro-2-ethylhexane Heptane 70 95.6 96

7680 1 -Chloro-2-ethylhexane Heptane 100 89.8 39 Reflux

7700 1 -Chloro-2-ethylhexane Cyclohexane 80 91.9 <10 Reflux

7741 1 -Chloro-2-ethylhexane Octane 125 44.4 Reflux

7754 1 -Chlorodecane Hexane 70 98.9 27 Reflux

7787 1 -Chlorododecane Hexane 70 100.0 20 Reflux

8044 1 -Chlorododecane Cyclopentane 50 78.4 461 Reflux

8046 1 -Chlorododecane Cyclopentane 50 82.3 146 Reflux, held for add. 3.5 hr reflux

8037 1 -Chlorododecane Toluene 60 81.8 71

8041 1 -Chlorododecane Toluene 80 88.5 27

8048 1 -Chlorododecane Toluene 110 59.4 34 Reflux